DE1209753B - Process for the production of polymeric organic boron-nitrogen compounds - Google Patents

Description

Process for the production of polymeric organic boron-nitrogen compounds The invention relates to a process for the production of polymeric organic Boron-nitrogen compounds, which is characterized in that one borazane the general formula R + BH3 in which R is a tertiary aliphatic, cycloaliphatic or aromatic amine or a mixed aliphatic cycloaliphatic-aromatic Amine or a heterocyclic nitrogen base means, with nitriles of the general Formula R1- (CN) n odel mixtures of these nitriles in which R1 is a hydrocarbon radical and n is an integer of at least 1, optionally in one opposite Solvents or suspending agents inert to the reactants, at temperatures above 100 "C converts.

With elimination of the amine component of the borazane, high molecular weight organic boron-nitrogen compounds obtained, for example, molecular weights of 500 and more.

Preference is given to using 1 mole of borazane per mole of nitrile group.

According to the invention, nian resins, pastes or oils have an amazing effect Have resistance and therefore as lubricants, lubricant additives and starting products can be used in the production of neutron absorbing materials.

Reactions between nitriles and boron compounds are known per se. Thus an unstable complex of the empirical is obtained from acetonitrile and diborane Formula CH3CN-BHa (Schlesinger, Burg, Chem. Rev., 31, p. 1 [1942]). It was too a reaction between acetonitrile and boron trifluoride was observed, also being a complex of the formula CH3CN BF3 resulted (Hoard, Owen, Buzz e 1, S a 1 m o n, Acta Cryst., 3, p. 121 [1950]). It is also known from aliphatic nitriles and diborane borazole (U.S. Patent 3,008,988).

However, no polymers were obtained by the known methods.

In the method according to the invention, their easy accessibility because of, preferably used: N-trimethyl-borazane, N-triethyl-borazane, N-tripropyl - borazan, N- diethyl - N - butyl - borazan, N - dimethyl - N - cyclohexyl - borazan, N - dimethyl -N-phenyl-borazane or pyridine-borane.

Examples of mononitriles are: acetonitrile, propionitrile, Butyronitrile, the nitriles of octanoic, dodecanoic and hexanoic acid, if appropriate ring-substituted hexahydrobenzoic acid nitriles, optionally ring-substituted ones Benzonitriles, e.g. B.

Benzonitrile, and optionally ring-substituted naphthonitriles.

Examples of compounds with several nitrile groups in the molecule are: Malonsäuredinitril, Glutarsäuredinitril, Adipinsäuredinitril, Cyanoform and 1,1,3,3-tetracyano propane.

The hydrocarbon radical carrying one or more nitrile groups can be saturated or aromatic, olefinically or acetylenically unsaturated. Puts one olefinically or acetylenically unsaturated compounds, such as. B. 1,4-dicyano-butene (2) or 1,1,2,2-tetracyanoethylene, takes place in addition to the reaction of borazane with the nitrile group under the conditions of the process according to the invention mostly still a hydroboration of the double or triple bond takes place, which often leads to a leads to additional crosslinking of the polymeric boron-nitrogen compound.

According to the invention, temperatures above 100 ° C. are used, with one at normal pressure, under foreign gas pressure (e.g. under nitrogen pressure) or else under the hydrogen pressure caused by the hydrogen split off during the reaction is conditional, can work.

The properties of those produced by the process of the invention Boron-containing polymers can also be largely influenced by the fact that man proceeds in a certain way during manufacture, e.g. B.

1. the nitrile and borazane components mixed and then heated to the reaction temperature at normal pressure or under pressure or 2. one the starting products are heated to the reaction temperature and then the other component z. B. via a dropping funnel or when working under pressure z. B. with the help of a Dosing pump feeds, or 3. the implementation in both 1 and under 2 mentioned embodiments carried out in an inert solvent or suspension medium. Benzene, toluene and xylene, for example, can be used for this purpose.

Example 1 In a stirrer, immersed thermometer, dropping funnel and a descending condenser, one puts 115 g (1 mol) of N-triethyl-borazane, dissolved in 500 ml of 1,2,4-trimethylbenzo1, pre-heated this mixture to about 145 0C and then drop in 117 g (1 mol) of benzyl cyanide within about 45 minutes. The contents of the flask change color to green, orange, Bright red finally intense red. One warms up 90 minutes at sump temperatures of about 1600C, the eliminated triethylamine is distilled and finally in a vacuum the 1,2,4-trimethylbenzene used as a solvent. After drying in vacuo 132 g of an intensely yellow-colored, soluble in benzene, CS2 and CCl4 are obtained Resin, the 6.9 01o boron, 9.8% nitrogen and 0.02% active hydrogen (gas volumetric determined by hydrolysis with half-concentrated warm sulfuric acid). The molecular weight determined ebullioscopy in benzene is 1500 A 100; the Melting point is around 165 "C.

EXAMPLE 2 A mixture consisting of 230 g (2 mol) of N-triethyl borazane and 234 g (2 mol) of benzyl cyanide is heated to 160 ° to 1700 ° C. for 3.5 hours in a 0.8 l capacity stirred autoclave flushed with nitrogen Sets a pressure of 100 at. After cooling to room temperature, the final pressure is 24 atm. The practically pure hydrogen (identified by gas chromatography) is blown off, the contents of the autoclave are transferred to a round bottom flask, the triethylamine split off from the N-triethylborazane is distilled, the residue is dried in vacuo and 250g are obtained of a yellow colored resin which is soluble in benzene, carbon tetrachloride, carbon disulfide, dioxane and tetrahydrofuran, which is 7.9 0% boron, 10.25 0% nitrogen and 0.02% active hydrogen Reaction conditions gtingen Experiment Nitrile used N-triethyl-borazane time | No. Triäthyi-borazan time ratur Amount of tight hours ° c 6 CH, - CN 123 g = 3 moles 345 g = 3 moles 3.5 170 7 -CN 258 g 2.5 moles 288 g = 2.5 moles 2,300 8 CN 153g = 1 mol 1 lSg = 1 mol 3 300 ½)) 9 N to C - (CHr3, -CN 162 g - 162 g: = - 1.5 mol g = 3 mol 2.5 160 10 NE CICHe-CH = CH-CH2-C3 N 106 g = 1 mole 345 g = 3 moles 1,250 contains. The molecular weight determined osmotically in tetrahydrofuran is 700; the melting point is around 205 ° C.

Example 3 173 g (1.5 mol) of N-triethyl borazane are added to a 0.8 liter autoclave and 176 g (1.5 moles) of benzyl cyanide mixed with 200 ml of benzene for 1 hour to 165 heated to 170 ° C with stirring. The reaction product is as in the previous examples described, worked up. One receives 192 g of a yellow, in z. B.

Benzene and tetrahydrofuran soluble resin containing 7.3% boron and 0.11% contains active hydrogen.

The molecular weight determined ebullioscopy in benzene is 2000 i 100; the melting point of the resin is around 175 ° C.

Example 4 In a 2.7-1 autoclave flushed with nitrogen 403 g (3.5 mol) of N-triethyl borazane heated to 180 ° C., 410 g within one hour (3.5 mol) benzyl cyanide is pumped evenly into the autoclave with the aid of a metering pump and then the reaction mixture is heated to 2000 ° C. for a further hour. It puts a pressure of 79 at. After cooling to room temperature, the final pressure is 20 at. The reaction product is worked up as described and 445 g of an orange Resin with 7.6% boron and 0.070 / 0 active hydrogen keep. The molecular weight, Determined ebullioscopically in benzene is 6000-1000. The substance changes color in a closed tube at temperatures of 260 ° light brown; up to 600 ° C could not Melting or sintering can be observed.

Example 5 In a 0.8 l stirred autoclave, a mixture of 21 g (0.2 mol) Benzonitrile, 211 g (1.8 mol) of benzyl cyanide and 230 g (2 mol) of N-triethylborazane The mixture was heated to 200 ° C. for 1.5 hours, a pressure of 130 atm being established. 230 g of a yellow resin which is soluble in benzene are obtained from the reaction product with 7.8% boron and 0.070 / 0 active hydrogen. That determined osmotically in benzene Molecular weight gave values of 874 and 851; the melting point is around 184 ° C.

A number of other nitriles were in a 0.8-1 autoclave with N-triethyl-borazane implemented analogously to Examples 3 and 5. The quantities used, the reaction conditions and the properties of the polymeric boron-nitrogen compounds obtained are summarized in the following table.

Here, 0 / o Ha = percentage of active hydrogen (hydridic hydrogen bound directly to boron), determined by gas volumetric hydrolysis with warm, half-concentrated sulfuric acid. Polymeric boron-nitrogen compounds Fp lot Color analysis soluble in e.g. B. Molecular Weight g ° C 158 egg yolks 16.4% B only a little in dioxane, - becomes light brown at 360 ° C, 21.85% N CS2, CCl4, Tetra- up to 600 ° C no sintering 0.35% Ha hydrofuran 267 gray, slightly 8.9% B; Benzene, Dioxane, 2000 # 100 ~ 72 yellowish tinged 11.6% N CS2, CCl4 (ebullioscopic in 0.220 / o Ha in benzene) 142 yellow-brown 7.6 0 / o B benzene, CS2 710 ~ 150 0.02% Ha (osmotic in benzene) 155 light yellow 14.8 0 /, B little in hot - becomes dark yellow at 3000 C, 19.150 / 0 N ethanol up to 6000 C no sintering 0.270 / 0 ha 138 gray, slightly 16.3 0 / o B difficult in warm CS2 - becomes gray-brown at 420 ° C yellowish | 0.14% Ha | | | no sintering up to 600 ° C Attempt | Starting substances | No time temperature Nitrile Nitrile amount N-triethyl-borazane hours ° C 11 coconut fatty acid nitrile of 293 g 173 g = 1.5 mol 2 300 medium composition C12.45 H25.9 C a N 12 C5H11 - C # N 146 g = 1.5 moles 173 g = 1.5 moles 2230 13 C17H35 - C # N 265 g = 1 mole 115 g = 1 mole 2.5 220 Reaction conditions Try starting substances No time temperature Nitrile Nitrile Amount To Borazan ß Amount Hours OC 14 C2H5 - CN 83 g = 1.5 moles N-cyclohexyl- 212 g = 1.5 moles 2.5 200 N, N-dimethyl borazan 15 CH8 - C m N 103 g = 2.5 moles N-phenyl-N, N-di- 338 g = 2.5 moles 3 170 to 180 methylborazane 16 C2H5 - CN 83 g = 1.5 moles pyridine borine 140 g = 1.5 moles 2190 to 200 diluted with 350ml benzene 17 C2H5 - CN 165 g = 3 mol N-triethylborazane 345 g = 3 mol 3.5 160

Claims (1)

Claim: Process for the production of polymeric organic boron-nitrogen compounds, characterized in that borazanes of the general formula R + BH3 in which R is a tertiary aliphatic, cycloaliphatic or aromatic amine or a mixed aliphatic - cycloaliphatic - aromatic amine Polymeric boron-nitrogen compounds Lot I properties g color analysis soluble in molecular weight 295 light brown 73.17% C benzene, hexane, CHCl3, 1150 d420 = 0.881 Oil 12.61% H CCl4, tetrahydrofuran (ebullioscopy in 4.95% B benzene) 6.810 / 0 N 8 # 20 ° = 608 cP 165 | light brown | 65.48% C | Benzene, ligroin, CHCl3, | 680 | d420 = 0.885 oil 12.12 0 / o H CCl4 (ebullioscopy in 8 20 ° = 312 cP 9.20 / 0 B benzene) 12,010 / o N 258 light gray; 77.17% C benzene, tetrahydrofuran, 1700 m.p. 40 ° C waxy 13.48% H CCl4, CHCl3 (ebullioscopic in 3.8% B benzene) Polymeric boron-nitrogen compounds, m.p. Amount of color analysis soluble in molecular weight 100 light yellow 48.48% C little in benzene - about 225 ° C 9.28% N 14.52% N 12.0% B. 0.04% Ha 102 yellow 46.07% C benzene, dioxane, ether, 8.63% H pyridine, CS2 20.75% N 15.8% B. 0.350 / 0 ha 102 dark yellow 49.850 / o C little in benzene - about 380 ° C 8.85% H. 17.55% N 11.33% B | | 127 yellow 48.81 0 / o C benzene 2000 about 175 ° C 9.43% H (cryoscopically in benzene) 19.40 / o N 13.53% B. or a mixed aliphatic-cycloaliphatic aromatic amine or a heterocyclic nitrogen base, with nitriles of the general formula R1 (CN) n or mixtures of these nitriles in which R1 is a hydrocarbon radical and n is an integer of at least 1, optionally in one opposite the reactants inert solvent or suspension medium, at temperatures above 100 ° C.